JP2008506814A - Polyalkyldiallylamine-epihalohydrin resin as wet paper strength enhancer for papermaking and method for producing the same - Google Patents

Abstract

  The present invention relates to a process for making polyalkyldiallylamine-epihalohydrin resins, the resulting resins, and aspects of their use as wet strength agents for papermaking. These resins are obtained by copolymerizing salts of alkyl diallylamine monomers and further reacting with epihalohydrins under carefully controlled reaction conditions.

Description

Background of the Invention
FIELD OF THE INVENTION This invention relates to a method for making polyalkyldiallylamine-epihalohydrin resins, the resulting resins, and their use as wet strength agents for papermaking.

Background Description and Other Information Polyamidoamine-epichlorohydrin resin (PAE resin), polyalkylene polyamine-epichlorohydrin resin (PAPAE resin), amine polymer-epichlorohydrin resin, polyurylene-epichloro Hydrin resins, polyamide-polyurylene-epichlorohydrin resins, and combinations of these resins with anionic polymers such as carboxymethylcellulose (CMC) have been widely used in the manufacture of paper with high levels of wet strength. It was.

  Of the epihalohydrin-containing resins, epoxide resins based on tertiary amines have the highest resin efficiency (generally higher levels of wet strength per unit mass added to paper or higher overall regardless of the amount of resin added) The highest off-machine wet strength (the ability to provide wet strength on a piece of paper without aging). This is in contrast to most other wet strength resins that show improvement in wet strength after several days of aging. Tertiary amine-based epoxide resins provide a high level of wet strength as made. Of the various types of tertiary amine based epoxide resins, polymethyldiallylamine-epichlorohydrin resin is the most effective wet strength agent known for paper on a wet basis. Some of these resins have already been described, as explained below.

  While polyalkyldiallylamine-epihalohydrin resins are known for their superior wet strength performance when compared to PAE resins, the methods used to make such resins are inefficient and therefore expensive. Aspects of the invention provide a method that allows for the production of polyalkyldiallylamine-epihalohydrin resins in a more cost effective manner.

  Polyalkyldiallylamine-epichlorohydrin resins and variants thereof are available in several US patents, such as US Pat. No. 3,686,151 (Keim); US Pat. No. 3,700,563 (Keim); US Pat. No. 3,772,076 (Keim); U.S. Pat. No. 3,833,531 (Keim); U.S. Pat. No. 4,229,321 (Van Eenam); U.S. Pat. No. 4,233,417 (Van Eenam); U.S. Pat. No. 4,298,639 (Van Eenam); Have been disclosed.

  Polymerization systems containing at least one quaternary amine monomer species are known in the art, but the initiation stage is at least three-component as described in US Pat. Nos. 3,700,563 and 3,833,531 (keim). Ie, a redox system comprising two reducing agents and one oxidizing agent; or as described in US Pat. No. 3,678,098 (Rohm and Haas Company), the redox system is a two-component system. Either consisting of only one oxidizing agent and one reducing agent, but not in combination with a quaternary amine. In these polymerization systems, one of the reducing agents is also added to the corresponding reaction mixture first, and the remaining components are added simultaneously, whereas the practice of the addition in the present invention is a two-component system. This eliminates the need to add one of the reducing agents in advance.

Further, typically in the art, after adding the first reducing agent, the weight (mass) ratio of the remaining two components to fully utilize the radical polymerization method is 1: 1. However, according to embodiments of the present invention, the weight ratio (or the corresponding molar ratio) of the duplex system can be significantly changed by greatly reducing the amount of oxidant used in the two-component system and still be a very effective catalyst. It becomes possible to obtain a system.
SUMMARY OF THE INVENTION The present invention relates to a process for making polyalkyldiallylamine-epihalohydrin resins, the resulting resins, and their use as wet strength agents for papermaking, wherein one aspect of the process is
(A) adding a salt of an alkyl diallylamine (ADAA) monomer to the water in the reactor to form an approximately 30-65% aqueous salt solution;
(B) purging the aqueous salt solution with an inert gas;
(C) heating the aqueous salt solution to a temperature of about 50 ° C. to about 80 ° C., preferably to steps (e) and (f);
(D) adding the redox initiator system to the aqueous salt solution under an inert atmosphere over about 2 to about 6 hours with stirring, preferably adding the redox initiator system continuously;
(E) Simultaneously with step (d), at least one comonomer is added to the aqueous salt solution with stirring under an inert atmosphere over about 2 to about 5 hours; thereby forming a copolymer, wherein the copolymer Has an RSV of from about 0.10 dL / g to about 0.45 dL / g, preferably from about 0.15 dL / g to about 0.25 dL / g, preferably at least one comonomer is continuously added;
(F) maintaining the contents of the container at about 50 ° C. to about 75 ° C. for a time of about 30 to about 120 minutes; diluting the copolymer with an amount of water, thereby providing about 9% to about 20%; Preferably forming a copolymer solution having a solids content of from about 9 to about 16%;
(G) adjusting the copolymer solution to a pH of about 7 to about 10, preferably about 7.5 to about 10, more preferably about 8 to about 10;
(H) To the copolymer solution is added epihalohydrin at a temperature of about 20 ° C. to about 50 ° C. in an amount to provide an epihalohydrin: polymer amine functionality ratio of about 0.85 to about 1.5; (J1) at the same time maintaining the pH at about 8 to about 10 and the temperature at about 20 ° C. to about 50 ° C. for a time of about 2 to about 8 hours; or (j2) at the same time initially adjusting the pH to about 8 to about 10 Adjusted to 10, allowing the pH to fluctuate as low as about 6.5, maintaining the temperature at about 20 ° C. to about 50 ° C. for a time of about 2 to about 8 hours; and (k) The temperature is raised to about 60 ° C. to about 90 ° C. over about 0.5 to about 4 hours, while sufficient acid is added to maintain the pH at about 1 to about 3.
Including that.

If desired, embodiments of the invention can further comprise steps (h1) to (h4), which are
(H1) heating the copolymer solution to a temperature of about 65 ° C. to about 75 ° C .;
(H2) The redox initiator as described above is added to the copolymer solution under an inert atmosphere over about 20 to about 35 minutes with stirring, wherein the redox initiator and copolymer are about 1:20 to In a weight percent ratio of about 1:80, more preferably the ratio is about 1:25, preferably the redox initiator is continuously added;
(H3) maintaining the contents of the vessel at about 65 ° C. to about 75 ° C. for a time of about 35 to about 75 minutes; and (h4) cooling the copolymer solution to ambient temperature.
Including that.

The present invention further relates to a resin which is a reaction product of the above method.
The invention further relates to the use of the resin as a wet paper strength enhancer, as well as to a cellulose matrix, preferably paper, containing the resin.
DETAILED DESCRIPTION OF THE INVENTION When numerical ranges are listed herein, the ranges are intended to encompass the endpoints and all integers and fractions within the ranges, unless otherwise specified. It is not intended that the scope of the various embodiments of the invention be limited to the specific values recited when defining a range. Further, all ranges described herein include not only the specific range specifically described, but also any combination of values within that range, for example, combinations of the minimum and maximum values listed. To do.

The present invention relates to a method for producing a polyalkyldiallylamine-epihalohydrin resin and an embodiment of the resulting resin, wherein one embodiment of the method comprises:
(A) Alkyl diallylamine (ADAA) monomer salt is added to the water in the reactor to provide about 30-65% aqueous salt solution, preferably about 35% to about 55% aqueous salt solution, more preferably about 40% to Forming about 45% aqueous salt solution, most preferably about 42% aqueous salt solution;
(B) purging the aqueous salt solution with an inert gas;
(C) heating the aqueous salt solution to a temperature of about 50 ° C. to about 80 ° C., preferably to steps (e) and (f);
(D) adding the redox initiator system to the aqueous salt solution under an inert atmosphere over about 2 to about 6 hours with stirring, preferably adding the redox initiator system continuously;
(E) Simultaneously with step (d), at least one comonomer is added to the aqueous salt solution with stirring under an inert atmosphere over about 2 to about 5 hours; thereby forming a copolymer, wherein the copolymer Has an RSV of from about 0.10 dL / g to about 0.45 dL / g, preferably from about 0.15 dL / g to about 0.25 dL / g, preferably at least one comonomer is continuously added;
(F) maintaining the contents of the container at about 50 ° C. to about 75 ° C. for a time of about 30 to about 120 minutes;
(G) diluting the copolymer with an amount of water, thereby forming a copolymer solution having a solids content of about 9% to about 20%;
(H) adjusting the copolymer solution to a pH of about 7 to about 10, preferably about 7.5 to about 10, more preferably about 8 to about 10;
(I) To the copolymer solution, epihalohydrin is added at a temperature of about 20 ° C. to about 50 ° C. in an amount to provide an epihalohydrin: polymer amine functional group ratio of about 0.85 to about 1.5; (J1) at the same time maintaining the pH at about 8 to about 10 and the temperature at about 20 ° C. to about 50 ° C. for a time of about 2 to about 8 hours; or (j2) at the same time initially adjusting the pH to about 8 to about 10 Adjusted to 10, allowing the pH to fluctuate as low as about 6.5, maintaining the temperature at about 20 ° C. to about 50 ° C. for a time of about 2 to about 8 hours; and (k) The temperature is raised to about 60 ° C. to about 90 ° C. over about 0.5 to about 4 hours, while sufficient acid is added to maintain the pH at about 1 to about 3.
Including that.

In addition, the process may optionally include stages (h1) to (h4) for burn-off of residual monomers, in which stage the copolymer solution is heated and an additional amount of Redox initiator is added to the copolymer solution (in an inert atmosphere, preferably under nitrogen) to reduce the balance of both monomer and comonomer. Steps (h1) to (h4) are used to reduce or remove residual comonomer, in particular acrylamide, when the copolymer solution is adjusted to a high pH value (typically 8-11, preferably 10). Useful. This optional step is advantageous because the amount of comonomer, particularly acrylamide, which is carcinogenic, is reduced, thus reducing the toxicity of the resulting resin. The optional steps (h1) to (h4) are not essential for obtaining sufficient wet strength results,
(H1) heating the copolymer solution to a temperature of about 65 ° C. to about 75 ° C .;
(H2) The redox initiator as described above is added to the copolymer solution under an inert atmosphere over about 20 to about 35 minutes with stirring, wherein the redox initiator and copolymer are about 1:20 to In a weight percent ratio of about 1:80, more preferably the ratio is about 1:25, preferably the redox initiator is continuously added;
(H3) maintaining the contents of the vessel at about 65 ° C. to about 75 ° C. for a time of about 35 to about 75 minutes; and (h4) cooling the copolymer solution to ambient temperature.
Including that.

For the synthesis of ADAA copolymers, copolymerization methods well known to those skilled in the art and generally described in G. Odian, Principles of Polymerization, Second Edition , Chapter 3, John Wiley & Sons, New York (1981), and Radical ring closure polymerization as described in GB Butler, Cyclopolymerization and Cyclocopolymerization , Marcel Dekker, New York (1992) is utilized.

  The copolymerization of the ADAA copolymer results in the formation of a cyclized copolymer backbone, which is referred to as “ring closure polymerization”. The cyclic backbone structure can be a 5- or 6-membered ring, or a mixture thereof. These structures are shown below:

[Wherein Z is a comonomer, and n and m represent the ratio of monomer to comonomer, for example, the ADAA salt and comonomer can be in a molar ratio of about 15:85 to about 45:55].

  Typically, a five-membered ring structure is the major repeating unit found in this type of copolymer, but the invention does not require a specific ring type or ratio. The relative amounts of the two structures include the identity and size of the substituent -R, the reaction temperature, the reaction solids, the specific initiator used, and the identity of the complexing acid. Depends on many factors. The -R group can be an alkyl group such as methyl, ethyl, propyl and butyl, wherein the alkyl group is small enough to maintain water solubility. The -R group can also be a hydroxyalkyl group or other type of substituted alkyl group.

  In order to produce a resin, and ultimately a paper or other cellulose matrix made using this resin, in an embodiment of the invention, a salt of an ADAA monomer prepared in an aqueous solution (eg, a hydrohalide salt) (hydrohalide salts), phosphates, sulfates and nitrates).

  In step (a), a salt of the alkyl diallylamine monomer or a mixture of various salts is added to the water in the reactor to give about 30-65% aqueous salt solution, preferably about 35% to about 55% aqueous salt solution, and more. Preferably about 40% to about 45% aqueous salt solution, most preferably about 42% aqueous salt solution is formed. Those skilled in the art will recognize and understand suitable methods for forming salts with complexing acids.

  Suitable complexing acids for forming ADAA monomer salts include hydrohalic acids such as hydrochloric acid, hydrobromic acid, hydroiodic acid, sulfuric acid, nitric acid, phosphoric acid, methanesulfonic acid and para-toluenesulfone. An acid etc. are mentioned.

  Suitable ADAA monomers for use in salt formation include N-methyldiallylamine (MDAA, methyldiallylamine), N-ethyldiallylamine (EDAA, ethyldiallylamine), Nn-propyldiallylamine (PDAA, propyldiallylamine), N -Isopropyldiallylamine, N-butyldiallylamine, N-tert-butyldiallylamine, N-sec-butyldiallylamine, N-pentyldiallylamine, Nn-hexyldiallylamine, N-acetamidodiallylamine, N-cyanomethyldiallylamine, N-β- Propionamide diallylamine, and N- (2-hydroxyethyl) diallylamine, and mixtures thereof include, but are not limited to. A preferred monomer is MDAA.

  Typically, the monomer has a high purity, but a wide range of purity can be used. For example, for MDAA, high purity is preferably at least about 98.5%, more preferably at least about 99.3%, and most preferably at least about 99.8%.

The monomers are copolymerized in the form of hydrohalides, preferably as hydrochlorides; phosphates, nitrates and sulfates.
Preferred hydrohalides include N-methyldiallylamine hydrochloride (MDAA · HCl), N-ethyldiallylamine hydrochloride (EDAA · HCl) and N-propyldiallylamine hydrochloride (PDAA · HCl). However, it is not limited to these.

  Preferred phosphates include, but are not limited to, methyl diallylammonium, ethyl diallylammonium, and propyl diallylammonium.

Preferred nitrates include, but are not limited to, methyl diallylammonium, ethyl diallylammonium, and propyl diallylammonium.
Preferred sulfates include, but are not limited to, methyldiallylammonium, ethyldiallylammonium, and propyldiallylammonium sulfate.

  In step (b), the aqueous salt solution should be purged with an inert gas, such as nitrogen or argon, to expel oxygen. These inert gases are commercially available and are used “as received” from the supplier. Purging is well known to those skilled in the art, where purging is preferably performed for at least about 45 minutes.

  In step (c), the aqueous salt solution is subsequently subjected to about 50 ° C. to about 80 ° C., preferably about 50 ° C. to about 70 ° C., more preferably about 55 ° C. to about 70 ° C., most preferably about 60 ° C. to about 65 ° C. Heat to the temperature of.

  In step (d), the polymerization of the copolymer is initiated by a redox (reduction-oxidation) catalyst system comprising two initiator solutions, wherein the first initiator solution contains a reducing agent, The initiator solution contains an oxidizer. In the catalyst system of the present invention, a dual catalyst system is used instead of a single thermally activated initiator, which catalyst system efficiently generates free radicals and subsequent polymerization at lower temperatures. Bring.

Typically, the reducing agent and oxidizing agent are used in a molar ratio of about 1: 0.1 to about 1: 1, preferably about 1: 0.1 to about 1: 0.9.
Examples of suitable oxidizing agents are peroxide type compounds, in particular salts of peroxydisulfuric acid such as sodium persulfate, potassium persulfate and ammonium persulfate, or other peroxide catalysts such as tert-butyl. Examples include, but are not limited to, hydroperoxides and hydrogen peroxide. The most preferred oxidizing agent is sodium peroxodisulfate (SPDS).

  Examples of suitable reducing agents used in conjunction with the above oxidizing agents include divalent or tetravalent sulfur compounds such as sulfides, sulfites, bisulfites, thiosulfates, hydrosulfites, metabisulfites. Salts, as well as other reducing salts, such as, but not limited to, sulfates of metals that can exist in a valence state greater than 1 such as cobalt, iron, manganese and copper. The most preferred reducing agent is sodium metabisulfite (SMBS).

  The redox catalyst system includes a combination of one reducing agent and one oxidizing agent. A preferred oxidizing agent is peroxydisulfate and the corresponding reducing agent is one of sulfite, bisulfite and metabisulfite. A more preferred oxidizing agent is sodium persulfate or ammonium persulfate, and a more preferred reducing agent is sodium bisulfite or sodium metabisulfite. Most preferably, the dual catalyst system comprises a combination of sodium persulfate (ie, sodium peroxodisulfate (SPDS)) and sodium metabisulfite.

  Generally, the redox initiator system is added continuously as an aqueous salt solution with stirring (preferably about 150-200 RPM) over a period of about 2 to about 6 hours. Overall, the feed period of the redox initiator system is preferably about 5 to about 30 minutes longer than the comonomer feed, and more preferably the additional feed time is about 10 to 20 minutes longer than the comonomer feed period. The aqueous salt solution should be kept under an inert atmosphere as defined above.

  The preferred continuous feed practice described herein is based on the simultaneous addition of comonomer and dual catalyst system. In general, simultaneous addition means that all components are flowing to the reactor at the same time without constant interruption. Further, when the supply of the comonomer is completed, the supply of the initiator solution is extended for a longer period than the supply period of the comonomer, and it continues for the predetermined period without interrupting the supply of the double catalyst system. Or it can be interrupted with the end of comonomer feed and resumed at a later point in time to meet the predetermined period of time. The feed rate is calculated by the formula 'number of feeds' divided by 'feed period', which is 187.0 g / 180 min = 1.039 g / min for the comonomer in Example 1 (Part 1), For the initiator solution it is 32.1 g / 190 min = 0.169 g / min. In this equation, since the supply period is a constant coefficient, it is only necessary to change the 'number of supply units' in order to change the scale of the process. Therefore, on a scale that is 1000 times larger, the supply rate is 1.039 kg / min for the comonomer and 0.169 kg / min for the catalyst solution, respectively.

  The dual catalyst initiator / monomer where the monomer includes both ADAA monomer and comonomer is generally in a molar ratio of about 1:35 to about 1: 185; preferably about 1:60 to about 1: 120; Most preferably, the ratio is 1:90.

  In step (e), which takes place simultaneously with the continuous addition of the redox initiator system, at least one comonomer is added to the heated salt solution under an inert atmosphere as defined above. The comonomer addition is performed over a period of about 2 hours to about 5 hours, preferably about 2.5 hours to about 4 hours, more preferably about 3.5 hours. As described in step (f), during continuous addition of the redox initiator and comonomer, the aqueous salt solution is about 50 ° C to about 75 ° C, preferably about 55 ° C to about 70 ° C, more preferably about 60 ° C to Maintained at a temperature of about 65 ° C .; after stopping the comonomer feed, at said temperature for a period of about 30 minutes to about 120 minutes, preferably about 40 minutes to about 120 minutes, more preferably about 60 minutes to about 120 minutes Should be maintained over time.

  The ADAA monomer is copolymerized with a water soluble comonomer. In general, at least one comonomer is used, which also contemplates the use of a mixture of two or more comonomers. Preferably, the ADAA monomer is, but is not limited to, vinyl monomers such as acrylamide, methacrylamide, acrylic acid, methacrylic acid, itaconic acid, alkyl (meth) acrylates such as methyl acrylate, methyl methacrylate. (MMA), ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, BMH, butyl acrylate (BA), butyl methacrylate, hydroxyalkyl (meth) acrylate, hydroxyethyl acrylate (HEA), hydroxyethyl methacrylate , Hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate (HBMA), styrene, ethylene, glyceryl acrylate and glyceryl methacrylate Hydroxypropyl methacrylamide (HPMA), and mixtures thereof; more preferably including acrylamide, methacrylamide, acrylic acid, methacrylic acid, itaconic acid, and mixtures thereof, most preferably acrylamide and acrylic acid and mixtures thereof Can be copolymerized with at least one comonomer.

  Typically, the ADAA salt and the at least one comonomer are in a molar ratio of about 15:85 to about 45:55, preferably 18:82 to about 40:60, and most preferably 34:66.

  Another method of preparing an ADAA copolymer with an appropriate reduced specific viscosity range is to start with a high molecular weight ADAA copolymer and reduce the molecular weight by shear energy or by use of ultrasound, each of which is well known to those skilled in the art. It is.

  The copolymer solution obtained from steps (a) to (f) should have a specific reduced specific viscosity (RSV). The desired RSV of the ADAA copolymer is not particularly limited, but is preferably about 0.10 to about 0.45 dL / g, preferably about 0.15 to about 0.30 dL / g, more preferably about 0.20 to about 0.25 dL / g, most preferably about 0.21 to about 0.23 dL / g.

In general, the reduced specific viscosity is determined by a two-stage method. First, the polymer solution flow time (PFT) is measured with a capillary viscometer. Here, the polymer solution has a set concentration. Second, the solvent flow time (SFT) is measured. In this way, the polymer flow time minus the solvent flow time divided by the solvent flow time ((PFT-SFT) / SFT = SV), thereby obtaining the specific viscosity. Next, the specific viscosity is obtained by dividing the specific viscosity by the polymer concentration. For example, RSV is measured by capillary viscometry of a 2.0 weight percent solution of polymer in 1.0 N NH ₄ Cl solution at 25 ° C.

  In step (g), the copolymer is diluted with an amount of water, thereby forming a copolymer solution having a solids content of about 9% to about 20%, preferably about 9% to about 16%. Those skilled in the art recognize that factors such as pH and temperature are interrelated and can be adjusted to provide the appropriate solids. Generally, the copolymer solution prior to dilution has a solids content of about 30% to about 50%, preferably about 35% to about 45%.

In step (h), the pH is adjusted with a base solution, preferably about 5% to about 15%, more preferably about 8 to about 11% aqueous sodium hydroxide (NaOH).
Steps (i) and either (j1) or (j2) involve the reaction of an ADAA copolymer with an epihalohydrin, preferably epichlorohydrin. Epihalohydrin is preferably added over a period of about 30 seconds, but may be added as quickly as possible.

  The amount of epihalohydrin to be mixed with the copolymer solution is about 0.85 to about 1.5, preferably about 0.95 to about 1.45; more preferably about 1.0 to about 1.45; Should provide a ratio of epihalohydrin to pADAA amine functionality of about 1.10 to about 1.20. In step (i), the copolymer / epihalohydrin solution should be maintained at a temperature of about 20 ° C to about 50 ° C.

  Concurrently with the temperature maintenance, the copolymer / epihalohydrin solution may vary in pH by either continuously adding the base during the reaction over a period of about 2 hours to about 8 hours or by adjusting the pH once at the start of the reaction. By allowing it to do so, a pH of about 8 to about 10 should be maintained. It is preferable to use an aqueous sodium hydroxide (NaOH) solution as described above for pH adjustment.

  One skilled in the art will know the range of pH, time and temperature as described above to prepare a resin having the desired properties, such as resin preparation time, residual level of epihalohydrin, and / or resin viscosity (molecular weight). , As well as using their relationship to each other will be recognized and understood. The parameters should be chosen in these predetermined ranges according to the RSV of the starting copolymer and the ratio of epihalohydrin to amine. This is because these factors have a significant effect on the reaction time of resin preparation. For example, a resin process that proceeds at a very fast rate cannot be easily controlled with respect to an increase in resin viscosity. This can lead to gelation of the resin, making it unsuitable for use. On the other hand, resin processes that take a fairly long time to increase viscosity are not suitable for commercial production of these resins (when the reaction time exceeds 24 hours).

  Following pH adjustment, in step (k), the temperature is from about 60 ° C. to about 90 ° C., preferably from about 70 ° C. to about 80 ° C., more preferably from about 70 ° C. to about 75 ° C .; Sufficient to maintain the pH in the range of about 1 to about 3, preferably about 2.5, over a period of about 4 hours, preferably about 1 hour to about 3 hours, more preferably about 2 hours to about 3 hours; Raise while adding amount of acid.

Suitable acids include sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid and hydrochloric acid. The preferred acid used is hydrochloric acid.
Generally, the residual ADAA monomer content is about 0.15% (1500 ppm) or less. The residual comonomer content is about 0.05% (500 ppm) or less.

  Application of an optional burn-out process step (eg, steps (h1)-(h4)) reduces the residual ADAA monomer content to an amount that is less than or equal to about 0.005% (50 ppm), and similarly reduces the residual comonomer content to about It becomes possible to reduce the amount to 0.001% (10 ppm) or less.

  Residual monomer content is typically high pressure liquid chromatography system (HPLC), eg, column material Zorbax Stablebond (SB-C18) 250 mm × 4.6 mm, particle size 5 μm, pore size 80 mm, USCL013425 (Agilent Technologies, Netherlands) ) Using a Waters 600 Controller, Waters column oven, Waters 486 Tunable Absorbance Detector (Waters, Netherlands) and Autosampler Dynamax model AI-200 Rainin (Varian, Netherlands).

  Residual ADAA monomer content is Perkin Elmer Autosystem XL gas chromatograph (Perkin Elmer, Netherlands) equipped with J & W column material, 60 m db-1, diameter 0.25 mm, film thickness 0.25 μm (Agilent Technologies, Netherlands) Is preferably measured by headspace analysis.

  The present invention avoids the use of organic solvents and organic chain transfer agents, which helps to handle toxic materials during the production cycle and reduce volatile organic compounds (VOC) present in the product. VOC reduction reduces air emissions and air pollution.

  The resulting polyADAA-epihalohydrin resins have significantly lower levels of residual epihalohydrin hydrolysis products than ever in paper products or other cellulose matrices made using these resins as wet paper strength enhancers. In general, the present invention provides a total concentration of epihalohydrin, 1,3-dihalopropanol (1,3-DHP), 2,3-dihalopropanol (2,3-DHP) and 3-halopropanediol (HPD). On the basis of a residue of epihalohydrin and epihalohydrin hydrolysis by-products in an amount of 3.0% or less.

The resin embodiment described herein is used as a wet strength agent for the method used to make a cellulose matrix, preferably paper. In general, the cellulose matrix preferably includes, but is not limited to, about 0.1 to about 3%, more preferably about 0.2% to about 1.5% resin by weight (active solids).
Examples The invention is further defined in the following examples. Here, all parts and percentages are by weight unless otherwise specified. While these examples illustrate preferred embodiments of the present invention, it should be understood that they are given by way of illustration only. From the above discussion and these examples, one of ordinary skill in the art can ascertain the substantial characteristics of the present invention and various changes and modifications to the present invention without departing from the spirit and scope thereof. Can be adapted to usage and conditions.

Example 1. Part 1: Synthesis of a copolymer of methyldiallylammonium chloride and acrylamide (18/82) A reactor equipped with a stirrer and a 64% aqueous solution of methyldiallylammonium chloride (66.6 g) and deionized water (32.1 g) Put in. The mixture was purged with high purity nitrogen gas for 45 minutes. Two aqueous initiator solutions (redox initiator system), 0.2 g sodium peroxodisulfate (SPDS) in 31.9 mL deionized water, and 1.8 g sodium metasulfite (SMBS) in 30.3 mL After dissolving in deionized water, both initiator solutions were prepared by purging with high purity N ₂ for 20 minutes. The stirrer was started, an adiabatic heating mantle Electromantel (EMC1000 / CE) was placed under the reaction flask, and the reaction mixture was heated to 60 ° C. controlled by Digital Controller MC810 (both manufactured by Electrothermal Engineering Ltd). While maintaining the N ₂ purge and holding the reaction at 60 ° C., SPDS / SMBS initiator solution and 50% aqueous solution of acrylamide (187 g) were added for 180 minutes for the acrylamide feed and for the redox initiator (SMBS / SPDS) feed. Added continuously to the reaction flask over 190 minutes. After all of the initiator solution was added, the reaction mixture was maintained at 60 ° C. for an additional 50 minutes.

The copolymer content of the product was 41% at pH 4.6 and the RSV of the copolymer was 0.337 dL / g.
Example 1. Part 2: Synthesis of pMDAA / AAM · HCl-epichlorohydrin resin Part 1 MDAA / AAM copolymer sample (65.0 g; copolymer RSV was 0.337 dL / g) and deionized water ( 50.0 g) was placed in a reactor equipped with a stirrer. While stirring at 200 rpm, the pH of the solution was adjusted from 4.15 to 8.51 using 5% aqueous NaOH (4.86 g). At this point, additional deionized water (50.0 g) was charged to the reactor and the temperature of the reaction mixture was 25 ° C. 5.96 g of epichlorohydrin was added to the mixture over 30 seconds. During the following 30 minutes, the temperature rose to 26 ° C. and the pH reached 8.76. Thereafter, an adiabatic heating mantle Electromantel (EMC0500 / CE) was placed under the reaction flask, and the reaction mixture was heated to 50 ° C. controlled by Digital Controller MC810 (both manufactured by Electrothermal Engineering Ltd). Gardner-Holt viscosity and pH were closely monitored throughout the synthesis of the resin. The pH dropped to 7.26 after the temperature reached 50 ° C. After 292 minutes, the Gardnerholt viscosity reached a value of “F” and the pH had dropped to 6.91. At this point, the pH was adjusted to about 2.0 by adding 17% aqueous HCl (0.5 g). The resin solution was then heated to 80 ° C. and additional 17% aqueous HCl was sent to the reaction mixture to maintain the pH at 2.0-2.5. The temperature was maintained at 80 ° C. for 1 hour and the pH was finally adjusted to 2.5. The total amount of 17% HCl aqueous solution used to adjust the pH at this stage was 3.65 g.

The total solids (oven method) of the final product was 18.1%.
Example 1. Part 3: Synthesis of pMDAA / AAM · HCl-epichlorohydrin resin Part 1 MDAA / AAM copolymer sample (65.0 g; copolymer RSV was 0.337 dL / g) and deionized water ( 50.0 g) was placed in a reactor equipped with a stirrer. While stirring at 200 rpm, the pH of the solution was adjusted from 4.27 to 8.51 using 5% aqueous NaOH (4.5 g). At this point, additional deionized water (50.0 g) was charged to the reactor and the temperature of the reaction mixture was 25 ° C. A 7.45 g portion of epichlorohydrin was added to the mixture over 30 seconds. During the next 30 minutes, the temperature rose to 27 ° C. and the pH reached 8.76. Thereafter, an adiabatic heating mantle Electromantel (EMC0500 / CE) was placed under the reaction flask, and the reaction mixture was heated to 50 ° C. controlled by Digital Controller MC810 (both manufactured by Electrothermal Engineering Ltd). Gardnerholt viscosity and pH were closely monitored throughout the synthesis of the resin. After 287 minutes, the Gardnerholt viscosity reached a value of “F” and the pH had dropped to 7.08. At this point, the pH was adjusted to about 2.0 by adding 17% aqueous HCl (0.5 g). The resin solution was then heated to 80 ° C. and additional 17% aqueous HCl was sent to the reaction mixture to maintain the pH at 2.0-2.5. The temperature was maintained at 80 ° C. for 1 hour and the pH was finally adjusted to 2.0. The total amount of 17% HCl aqueous solution used to adjust the pH at this stage was 4.58 g.

The total solids (oven method) of the final product was 18.4%.
Example 2 Part 1: Synthesis of copolymer of methyldiallylammonium chloride and acrylamide (30/70) After charging 25.3 g of methyldiallylamine and 50.0 g of deionized water, the reactor was cooled in an ice bath. The temperature was maintained below 20 ° C. using an ice bath. Using an addition funnel, 22.8 g of 36% hydrochloric acid (HCl) was slowly added to the stirred reactor. The addition rate was adjusted to maintain the temperature of the reaction mixture at 12-15 ° C. At the end of the addition of the HCl solution, the ice bath was removed and the reaction mixture was stirred at ambient temperature for 1 hour. At this point, the reaction mixture was a clear light yellow solution. The mixture was then purged with high purity nitrogen gas for 45 minutes. Two aqueous initiator solutions (redox initiator system) 0.1 g sodium peroxodisulfate (SPDS) in 16.9 mL deionized water and 0.7 g sodium metasulfite (SMBS) 16.3 mL After dissolving in deionized water, both initiator solutions were prepared by purging with high purity N ₂ for 20 minutes. The stirrer was started, an adiabatic heating mantle Electromantel (EMC1000 / CE) was placed under the reaction flask, and the reaction mixture was heated to 60 ° C. controlled by Digital Controller MC810 (both manufactured by Electrothermal Engineering Ltd). SPDS / SMBS initiator solution and 50% aqueous solution of acrylamide (74.6 g) were added to the acrylamide feed for 178 minutes while maintaining the N ₂ purge and the reaction held at 60 ° C. (SMBS / SPDS) The feed was continuously added to the reaction flask over 186 minutes. After all of the initiator solution was added, the reaction mixture was maintained at 60 ° C. for an additional hour.

The copolymer content of the product was 36.4% at pH 4.7 and the RSV of the copolymer was 0.408 dL / g.
Example 2 Part 2: Synthesis of pMDAA / AAM · HCl-epichlorohydrin resin Part 1 MDAA / AAM copolymer sample (65.0 g; copolymer RSV was 0.408 dL / g) and deionized water ( 80.0 g) was placed in a reactor equipped with a stirrer. While stirring at 200 rpm, the pH of the solution was adjusted from 4.4 to 8.5 using 5% aqueous NaOH (5.9 g). At this point, additional deionized water (28.0 g) was charged to the reactor and the temperature of the reaction mixture was 24 ° C. 7.86 g of epichlorohydrin was added to the mixture over 30 seconds. During the next 30 minutes, the temperature rose to 28 ° C. and the pH had reached 8.71. Thereafter, an adiabatic heating mantle Electromantel (EMC0500 / CE) was placed under the reaction flask, and the reaction mixture was heated to 50 ° C. controlled by Digital Controller MC810 (both manufactured by Electrothermal Engineering Ltd). Gardnerholt viscosity and pH were closely monitored throughout the synthesis of the resin. The pH had dropped to 7.1 after the temperature reached 49 ° C. After 165 minutes, the Gardnerholt viscosity reached a value of “D” and the pH had dropped to 6.97. At this point, the pH was adjusted to about 2.0 by adding 17% aqueous HCl (0.5 g). The resin solution was then heated to 80 ° C. and additional 17% aqueous HCl was sent to the reaction mixture to maintain the pH at 2.0-2.5. The temperature was maintained at 80 ° C. for 1 hour and the pH was finally adjusted to 2.34. The total amount of 17% HCl aqueous solution used to adjust the pH at this stage was 4.45 g.

The total solids (oven method) of the final product was 15.7%.
Example 3 Part 1: Synthesis of a copolymer of methyldiallylammonium chloride and acrylamide (34/66) A 65% aqueous solution of methyldiallylammonium chloride (189.6 g) and deionized water (81.8 g) were equipped with a stirrer. Put it in. The mixture was purged with high purity nitrogen gas for 45 minutes. Two aqueous initiator solutions (redox initiator system), 0.3 g sodium peroxodisulfate (SPDS) in 48.8 mL deionized water, and 2.3 g sodium metasulfite (SMBS) in 46.7 mL After dissolving in deionized water, both initiator solutions were prepared by purging with high purity N ₂ for 20 minutes. The stirrer was started, an adiabatic heating mantle Electromantel (EMC1000 / CE) was placed under the reaction flask, and the reaction mixture was heated to 60 ° C. controlled by Digital Controller MC810 (both manufactured by Electrothermal Engineering Ltd). SPDS / SMBS initiator solution and 50% aqueous solution of acrylamide (230.3 g) were added to the redox initiator (SMBS / SPDS) for 180 minutes with respect to the acrylamide feed while maintaining the N ₂ purge and holding the reaction at 60 ° C. Added continuously to the reaction flask over 190 minutes for feeding. After all of the initiator solution was added, the reaction mixture was maintained at 60 ° C. for an additional 50 minutes.

The copolymer content of the product was 41.5% at pH 4.8 and the RSV of the copolymer was 0.338 dL / g.
Example 3 Part 2: Synthesis of pMDAA / AAM · HCl-epichlorohydrin resin Part 1 MDAA / AAM copolymer sample (538.4 g; copolymer RSV was 0.338 dL / g) and deionized water ( 800.0 g) was placed in a reactor equipped with a stirrer. While stirring at 200 rpm, the pH of the solution was adjusted from 5.55 to 8.5 using 5% aqueous NaOH (55.6 g). At this point, additional deionized water (374.7 g) was charged to the reactor and the temperature of the reaction mixture was 25 ° C. 103.96 g of epichlorohydrin was added to the mixture over 30 seconds. During the following 37 minutes, the temperature rose to 30 ° C. and the pH reached 8.76. Thereafter, an adiabatic heating mantle Electromantel (EMC0500 / CE) was placed under the reaction flask, and the reaction mixture was heated to 50 ° C. controlled by Digital Controller MC810 (both manufactured by Electrothermal Engineering Ltd). Gardnerholt viscosity and pH were closely monitored throughout the synthesis of the resin. The pH dropped to 7.63 after the temperature reached 45 ° C. After 369 minutes, the Gardnerholt viscosity reached a value of “D” and the pH had dropped to 7.04. At this point, the pH was adjusted to about 1.0 by adding 17% aqueous HCl (41.6 g).

  The resin contained undetectable ppm (ND ppm) epichlorohydrin, 2.3% 1,3-DCP, 108 ppm 2,3-DCP and 4500 ppm CPD. The total solids (oven method) of the final product was 15.8%.

Example 4 Part 1: Synthesis of a copolymer of methyldiallylammonium chloride and acrylamide (34/66) A 65% aqueous solution (191.8 g) of methyldiallylammonium chloride and deionized water (89.4 g) were equipped with a stirrer. Put in. The mixture was purged with high purity nitrogen gas for 45 minutes. Two aqueous initiator solutions (redox initiator system), 0.6 g sodium peroxodisulfate (SPDS) in 49.1 mL deionized water, and 4.7 g sodium metasulfite (SMBS) in 44.9 mL After dissolving in deionized water, both initiator solutions were prepared by purging with high purity N ₂ for 20 minutes. The stirrer was started, an adiabatic heating mantle Electromantel (EMC1000 / CE) was placed under the reaction flask, and the reaction mixture was heated to 70 ° C. controlled by Digital Controller MC810 (both manufactured by Electrothermal Engineering Ltd). SPDS / SMBS initiator solution and 50% aqueous solution of acrylamide (233 g) are maintained for 200 minutes for acrylamide feed and for redox initiator (SMBS / SPDS) feed while maintaining N ₂ purge and holding the reaction at 70 ° C. Added continuously to the reaction flask over 210 minutes. After all of the initiator solution was added, the reaction mixture was maintained at 70 ° C. for an additional 50 minutes.

  The copolymer content of the product was 41.8% at pH 5.5 and the RSV of the copolymer was 0.229 dL / g. The residual levels at pH 5.5 were 35 ppm for acrylamide and 1400 ppm for methyldiallylamine, respectively.

Example 4 Part 2: Synthesis of pMDAA / AAM · HCl-epichlorohydrin resin Part 1 MDAA / AAM copolymer sample (110.0 g; RSV of copolymer was 0.229 dL / g) and deionized water ( 240.0 g) was placed in a reactor equipped with a stirrer. While stirring at 200 rpm, the pH of the solution was adjusted from 5.06 to 8.58 using 10% aqueous NaOH (5.48 g). At this point, the temperature of the reaction mixture was 21 ° C. 16.81 g of epichlorohydrin was added to the mixture over 30 seconds. The reaction was then heated to 40 ° C. and the Gardnerholt viscosity and pH were monitored. The pH was maintained at 8.0-8.5 by incremental addition of 8% aqueous NaOH. A total of 32.5 g of 8% aqueous NaOH was added over 110 minutes. After 134 minutes, the Gardnerholt viscosity reached a value of “D”. At this point, the pH was adjusted to about 2.0 by adding 17% aqueous HCl (10.94 g). The resin solution was then heated to 75 ° C. and additional 17% aqueous HCl was sent to the reaction mixture to maintain the pH at 1.0-2.0. The temperature was maintained at 75 ° C. for 2 hours and the pH was finally adjusted to 1.95. The total amount of 17% HCl aqueous solution used to adjust the pH at this stage was 24.09 g.

  The resin contained 19 ppm epichlorohydrin, 0.88% 1,3-DCP, 149 ppm 2,3-DCP and 2240 ppm CPD. The total solid content (oven method) of the final product was 15.0%. The residual levels at pH 1.95 were 219 ppm for acrylamide and 222 ppm for methyldiallylamine, respectively.

Example 5 FIG. Part 1: Synthesis of copolymer of methyldiallylammonium phosphate and acrylamide (39/61) A 58.3% aqueous solution of methyldiallylammonium phosphate (262.4 g) and deionized water (100 g) were added to a reactor equipped with a stirrer. Put in. The mixture was purged with high purity nitrogen gas for 45 minutes. Two aqueous initiator solutions (redox initiator system), 0.7 g sodium peroxodisulfate (SPDS) in 36.8 mL deionized water, and 5.3 g sodium metasulfite (SMBS) in 32.1 mL After dissolving in deionized water, both initiator solutions were prepared by purging with high purity N ₂ for 20 minutes. The stirrer was started, an adiabatic heating mantle Electromantel (EMC1000 / CE) was placed under the reaction flask, and the reaction mixture was heated to 70 ° C. controlled by Digital Controller MC810 (both manufactured by Electrothermal Engineering Ltd). SPDS / SMBS initiator solution and 50% aqueous solution of acrylamide (162.6 g) were added to the acrylamide feed for 200 minutes while maintaining the N ₂ purge and the reaction held at 70 ° C. (SMBS / SPDS) The addition to the reaction flask was continued over 210 minutes for feeding. After all of the initiator solution was added, the reaction mixture was maintained at 70 ° C. for an additional hour.

The copolymer content of the product was 40.7% at pH 4.4 and the RSV of the copolymer was 0.131 dL / g.
Example 5 FIG. Part 2: Synthesis of pMDAA / AAM.H ₃ PO ₄ -epichlorohydrin resin Part 1 MDAA / AAM copolymer sample (110.0 g; RSV of copolymer was 0.131 dL / g) Ionized water (200.0 g) was placed in a reactor equipped with a stirrer. While stirring at 200 rpm, the pH of the solution was adjusted from 4.3 to 8.5 using 10% aqueous NaOH (59.1 g). At this point, the temperature of the reaction mixture was 25 ° C. 11.17 g of epichlorohydrin was added to the mixture over 30 seconds. The reaction was then heated to 40 ° C. and the Gardnerholt viscosity and pH were monitored. The pH was maintained between 8.45 and 8.55 by incrementally adding 8% aqueous NaOH using the stat function of a titrator (DL53 Titrator from Mettler Toledo). A total of 37.4 g of 8% aqueous NaOH was added over 248 minutes. After 270 minutes, the Gardnerholt viscosity reached a value of “D”. At this point, the reaction was stopped by adding 17% aqueous HCl (13.39 g). The resin solution was then heated to 75 ° C. and additional 17% aqueous HCl was sent to the reaction mixture to maintain the pH at 1.5-2.0. The temperature was maintained at 75 ° C. for 2 hours and the pH was finally adjusted to 2.0. The total amount of 17% HCl aqueous solution used to adjust the pH at this stage was 43.06 g.

  The resin contained undetectable ppm epichlorohydrin, 1200 ppm 1,3-DCP, 15 ppm 2,3-DCP and 808 ppm CPD. The total solids (oven method) of the final product was 14.7%.

Example 6 Part 1: Synthesis of a copolymer of methyldiallylammonium sulfate and acrylamide (39/61) A 52% aqueous solution of methyldiallylammonium sulfate (278.6 g) and deionized water (65 g) were equipped with a stirrer. Put in. The mixture was purged with high purity nitrogen gas for 45 minutes. Two aqueous initiator solutions (redox initiator system), 0.7 g sodium peroxodisulfate (SPDS) in 45.8 mL deionized water, and 5.5 g sodium metasulfite (SMBS) in 41 mL deionized water. After dissolving in ionic water, both initiator solutions were prepared by purging with high purity N ₂ for 20 minutes. The stirrer was started, an adiabatic heating mantle Electromantel (EMC1000 / CE) was placed under the reaction flask, and the reaction mixture was heated to 70 ° C. controlled by Digital Controller MC810 (both manufactured by Electrothermal Engineering Ltd). SPDS / SMBS initiator solution and 50% aqueous solution of acrylamide (201.4 g) were added to the acrylamide feed for 200 minutes while maintaining the N ₂ purge and the reaction held at 70 ° C. (SMBS / SPDS) The addition to the reaction flask was continued over 210 minutes for feeding. After all of the initiator solution was added, the reaction mixture was maintained at 70 ° C. for an additional hour.

The copolymer content of the product was 40.3% at pH 4.5 and the RSV of the copolymer was 0.191 dL / g.
Example 6 Part 2: Synthesis of pMDAA / AAM.H ₂ SO ₄ -epichlorohydrin resin Part 1 MDAA / AAM copolymer sample (95.0 g; RSV of copolymer was 0.191 dL / g) Ionized water (192.0 g) was placed in a reactor equipped with a stirrer. While stirring at 200 rpm, the pH of the solution was adjusted from 4.32 to 8.55 using 8% aqueous NaOH (3.98 g). At this point, the temperature of the reaction mixture was 21 ° C. 14.98 g of epichlorohydrin was added to the mixture over 30 seconds. The reaction was then heated to 40 ° C. and the Gardnerholt viscosity and pH were monitored. The pH was maintained at 8.45 to 8.55 by incrementally adding 8% aqueous NaOH using DL53 Titrator (Mettler Toledo). A total of 44.25 g of 8% aqueous NaOH was added over 143 minutes. After 192 minutes, the Gardnerholt viscosity reached a value of “D”. At this point, the pH was adjusted from 8.06 to about 2.0 by adding 17% aqueous HCl (10.83 g). The resin solution was then heated to 75 ° C. and additional 17% aqueous HCl was sent to the reaction mixture to maintain the pH at 1.5-2.0. The temperature was maintained at 75 ° C. for 1 hour and 40 minutes and the pH was finally adjusted to 2.0. The total amount of 17% HCl aqueous solution used to adjust the pH at this stage was 23.87 g.

  This resin contained undetectable ppm epichlorohydrin, 0.66% 1,3-DCP, 132 ppm 2,3-DCP and 3217 ppm CPD. The total solids (oven method) of the final product was 15.5%.

Example 7 Part 1: Synthesis of a copolymer of ethyl diallylammonium chloride and acrylamide (34/66) A 50% aqueous solution of ethyl diallylammonium chloride (259.4 g) and deionized water (44.7 g) were added to a reactor equipped with a stirrer. Put in. The mixture was purged with high purity nitrogen gas for 45 minutes. Two aqueous initiator solutions (redox initiator system), 0.84 g sodium peroxodisulfate (SPDS) in 46.4 mL deionized water, and 6.73 g sodium metasulfite (SMBS) in 40.5 mL After dissolving in deionized water, both initiator solutions were prepared by purging with high purity N ₂ for 20 minutes. The stirrer was started, an adiabatic heating mantle Electromantel (EMC1000 / CE) was placed under the reaction flask, and the reaction mixture was heated to 60 ° C. controlled by Digital Controller MC810 (both manufactured by Electrothermal Engineering Ltd). While maintaining the N ₂ purge and holding the reaction at 60 ° C., SPDS / SMBS initiator solution and 50% aqueous solution of acrylamide (213.8 g, adjusted to pH 3.1) were added over 240 minutes for the acrylamide feed. Added continuously to the reaction flask. The supply of the initiator solution was first interrupted with the end of the acrylamide supply, and resumed for another 12 minutes after 60 minutes while maintaining the temperature at 60 ° C. (total supply time at the end of 252 minutes). After all of the initiator solution was added, the reaction mixture was maintained at 60 ° C. for an additional 48 minutes and then cooled to room temperature.

The copolymer content of the product was 41.4% at pH 2.9 and the RSV of the copolymer was 0.176 dL / g.
Example 7 Part 2: Synthesis of pEDAA / AAM.HCl-epichlorohydrin resin Part 1 Sample of EDAA / AAM copolymer (110.0 g; RSV of copolymer was 0.176 dL / g) and deionized water ( 240.0 g) was placed in a reactor equipped with a stirrer. While stirring at 200 rpm, the pH of the solution was adjusted to about 9.0 using 11% aqueous NaOH (9.59 g). At this point, the temperature of the reaction mixture was 22 ° C. 16.37 g of epichlorohydrin was added to the mixture over 30 seconds. The reaction was then heated to 40 ° C. and the Gardnerholt viscosity and pH were monitored. The pH was maintained at about 8.5 for about 220 minutes and about 9.5 for about 45 minutes by incremental addition of 11% aqueous NaOH (39.9 g). After 265 minutes, the Gardnerholt viscosity reached the value of “D” and the pH was adjusted to about 2.0 by adding 18% aqueous HCl (2.9 g). The resin solution was then heated to 75 ° C. and additional 18% aqueous HCl was sent to the reaction mixture to maintain the pH at 2.0-3.0. The temperature was maintained at 75 ° C. for 75 minutes and the pH was finally adjusted to 2. The total amount of 18% HCl aqueous solution used to adjust the pH at this stage was 29.8 g.

  The resin contained undetectable ppm epichlorohydrin, 0.87% 1,3-DCP, 155 ppm 2,3-DCP and 2688 ppm CPD. The total solids (oven method) of the final product was 15.1%.

Example 8 FIG. Part 1: Synthesis of a copolymer of ethyl diallylammonium nitrate and acrylamide (34/66) A 50% aqueous solution of ethyl diallylammonium nitrate (291.5 g) and deionized water (53.5 g) were equipped with a stirrer. Placed in reactor. The mixture was purged with high purity nitrogen gas for 45 minutes. Two aqueous initiator solutions (redox initiator system), 0.81 g sodium peroxodisulfate (SPDS) in 44.7 mL deionized water, and 6.5 g sodium metasulfite (SMBS) in 39.1 mL After dissolving in deionized water, both initiator solutions were prepared by purging with high purity N ₂ for 20 minutes. The stirrer was started, an adiabatic heating mantle Electromantel (EMC1000 / CE) was placed under the reaction flask, and the reaction mixture was heated to 60 ° C. controlled by Digital Controller MC810 (both manufactured by Electrothermal Engineering Ltd). While maintaining the N ₂ purge and holding the reaction at 60 ° C., SPDS / SMBS initiator solution and 50% aqueous solution of acrylamide (213.8 g, adjusted to pH 3.1) were added over 240 minutes for the acrylamide feed. Added continuously to the reaction flask. The supply of the initiator solution was first interrupted with the end of the acrylamide supply and resumed for another 10 minutes after 60 minutes while maintaining the temperature at 60 ° C. (total supply time at the end of 250 minutes). After all of the initiator solution was added, the reaction mixture was maintained at 60 ° C. for an additional 50 minutes and then cooled to room temperature.

The copolymer content of the product was 41.3% at pH 4.0 and the RSV of the copolymer was 0.139 dL / g.
Example 8 FIG. Part 2: Synthesis of pEDAA / AAM · HNO ₃ -epichlorohydrin resin Part 1 EDAA / AAM copolymer sample (110.0 g; copolymer RSV was 0.139 dL / g) and deionized water (230.0 g) was placed in a reactor equipped with a stirrer. While stirring at 200 rpm, the pH of the solution was adjusted to about 9.0 using 11% aqueous NaOH (7.42 g). At this point, the temperature of the reaction mixture was 22 ° C. A 15.02 g portion of epichlorohydrin was added to the mixture over 30 seconds. The reaction was then heated to 40 ° C. and the Gardnerholt viscosity and pH were monitored. The pH was maintained at about 9.0 by incremental addition of 11% aqueous NaOH (37.6 g). After 330 minutes, the Gardnerholt viscosity reached a value of “D” and the pH was adjusted to about 2.0 by adding 18% aqueous HCl (3.4 g). The resin solution was then heated to 75 ° C. and additional 18% aqueous HCl was sent to the reaction mixture to maintain the pH between 2.0 and 2.5. The temperature was maintained at 75 ° C. for 47 minutes and the pH was finally adjusted to 2.10. The total amount of 18% HCl aqueous solution used to adjust the pH at this stage was 17.3 g.

  The resin contained 11 ppm epichlorohydrin, 0.64% 1,3-DCP, 117 ppm 2,3-DCP and 3782 ppm CPD. The total solids (oven method) of the final product was 15.5%.

Example 9 Part 1: Synthesis of copolymer of propyl diallylammonium nitrate and acrylamide (34/66) A 50% aqueous solution of propyl diallylammonium nitrate (300.7 g) and deionized water (56.5 g) were equipped with a stirrer. Placed in reactor. The mixture was purged with high purity nitrogen gas for 45 minutes. Two aqueous initiator solutions (redox initiator system), 0.78 g sodium peroxodisulfate (SPDS) in 42.9 mL deionized water, and 6.24 g sodium metasulfite (SMBS) in 37.5 mL After dissolving in deionized water, both initiator solutions were prepared by purging with high purity N ₂ for 20 minutes. The stirrer was started, an adiabatic heating mantle Electromantel (EMC1000 / CE) was placed under the reaction flask, and the reaction mixture was heated to 60 ° C. controlled by Digital Controller MC810 (both manufactured by Electrothermal Engineering Ltd). The SPDS / SMBS initiator solution and a 50% aqueous solution of acrylamide (205.3 g, adjusted to pH 3.0) were reacted for 240 minutes with respect to the acrylamide feed while maintaining the N ₂ purge and holding the reaction at 60 ° C. Added continuously to the flask. The supply of the initiator solution was first interrupted with the end of the acrylamide supply and resumed for another 10 minutes after 60 minutes while maintaining the temperature at 60 ° C. (total supply time at the end of 250 minutes). After all of the initiator solution was added, the reaction mixture was maintained at 60 ° C. for an additional 50 minutes and then cooled to room temperature.

The copolymer content of the product was 41.2% at pH 4.3 and the RSV of the copolymer was 0.123 dL / g.
Example 9 Part 2: Synthesis of pPDAA / AAM.HNO ₃ -epichlorohydrin resin Part 1 PDAA / AAM copolymer sample (110.0 g; copolymer RSV was 0.123 dL / g) and deionized water (230.0 g) was placed in a reactor equipped with a stirrer. While stirring at 200 rpm, the pH of the solution was adjusted to about 8.6 using 11% aqueous NaOH (3.54 g). At this point, the temperature of the reaction mixture was 22 ° C. 14.39 g of epichlorohydrin was added to the mixture over 30 seconds. The reaction was then heated to 40 ° C. and the Gardnerholt viscosity and pH were monitored. The pH was maintained at about 9.0 by incremental addition of 11% aqueous NaOH (42.65 g). After 362 minutes, the Gardnerholt viscosity reached the value of “D” and the pH was adjusted to about 2.0 by adding 18% aqueous HCl (3.3 g). The resin solution was then heated to 75 ° C. and additional 18% aqueous HCl was sent to the reaction mixture to maintain the pH between 2.0 and 2.5. The temperature was maintained at 75 ° C. for 140 minutes and the pH was finally adjusted to 2.2. The total amount of 18% HCl aqueous solution used to adjust the pH at this stage was 20.2 g.

  The resin contained <10 ppm epichlorohydrin, 0.55% 1,3-DCP, 95 ppm 2,3-DCP and 3050 ppm CPD. The total solids (oven method) of the final product was 15.4%.

Example 10 Part 1: Synthesis of a copolymer of methyldiallylammonium chloride and acrylamide (34/66) A reactor equipped with a stirrer and a 50% aqueous solution of methyldiallylammonium chloride (260.2 g) and deionized water (42.9 g) Put in. The mixture was purged with high purity nitrogen gas for 45 minutes. Two aqueous initiator solutions (redox initiator system), 0.9 g sodium peroxodisulfate (SPDS) in 50.9 mL deionized water, and 7.4 g sodium metasulfite (SMBS) in 44.5 mL After dissolving in deionized water, both initiator solutions were prepared by purging with high purity N ₂ for 20 minutes. The stirrer was started, an adiabatic heating mantle Electromantel (EMC1000 / CE) was placed under the reaction flask, and the reaction mixture was heated to 60 ° C. controlled by Digital Controller MC810 (both manufactured by Electrothermal Engineering Ltd). A 50% aqueous solution of SPDS / SMBS initiator solution and acrylamide (243.2 g) (adjusted to pH 3.12 with 36% aqueous HCl) was maintained while maintaining the N ₂ purge and maintaining the reaction at 60 ° C. Continuously added to the reaction flask over 244 minutes for feed and 250 minutes for redox initiator (SMBS / SPDS) feed. Initiator feed was temporarily interrupted at the end of acrylamide feed and resumed for another 7 minutes after 60 minutes. After all the initiator solution was added, the reaction mixture was maintained at 60 ° C. for an additional 53 minutes.

  The copolymer content of the product was 41.9% at pH 3.6 and the RSV of the copolymer was 0.243 dL / g. The residual levels at pH 3.6 were 108 ppm for acrylamide and <122 ppm for methyl diallylamine, respectively.

A 14% solution of the same copolymer, adjusted to pH 11 prior to residue analysis, showed an acrylamide residue level of 126 ppm.
Example 10 Part 2: Synthesis of pMDAA / AAM · HCl-epichlorohydrin resin Part 1 MDAA / AAM copolymer sample (110.0 g; copolymer RSV was 0.243 dL / g) and deionized water ( 240.0 g) was placed in a reactor equipped with a stirrer (under a constant N ₂ atmosphere). While stirring at 200 rpm, the pH of the solution was adjusted from 3.5 to 10.0 using 11% aqueous NaOH (30.26 g). At this point, the temperature of the reaction mixture was 22 ° C. The polymer solution was then heated to 75 ° C. At this point, a 1% aqueous solution (15.1 g) of sodium peroxodisulfate (SPDS) and a 10% solution of sodium metasulfite (SMBS) (16.65 g) were added to the polymer mixture over 30 minutes. After completing the supply of the SMBS / SPDS initiator, the temperature of the reaction solution was maintained at 75 ° C. for an additional 38 minutes, and then cooled to room temperature. 17.39 g of epichlorohydrin was added to the mixture over 30 seconds. The reaction mixture was maintained at a temperature of about 23 ° C. and the Gardnerholt viscosity and pH were monitored. After 109 minutes, the Gardnerholt viscosity reached a value of “E”. At this point, the pH was adjusted from 8.8 to about 2.0 by adding 18% aqueous HCl (3.37 g). The resin solution was then heated to 75 ° C. and additional 18% aqueous HCl was sent to the reaction mixture to maintain the pH at 2.0-3.0. The temperature was maintained at 75 ° C. for 1 hour and 20 minutes, and the pH was finally adjusted to about 2.4. The total amount of 18% HCl aqueous solution used in the resin stabilization step was 19.7 g.

  The resin contained 14 ppm epichlorohydrin, 0.76% 1,3-DCP, 75 ppm 2,3-DCP and 1353 ppm CPD. The total solids (oven method) of the final product was 15%. The acrylamide level at pH 2.4 was 1 ppm. Residual levels at pH 10 were 8 ppm for acrylamide and <42 ppm for methyldiallylamine, respectively.

Example 11 Evaluation of paper strength Pilot papermaking at pH 7.5 using a 50:50 blend of softwood / hardwood bleached kraft pulp beaten to a Shopper-Riegel number of 36 ° (or its Canadian standard freeness) Paper was made with a machine (type: Officine Meccaniche Toschi; SpA (Lucca) Marlia (Italy)). A paper containing 1.0% treated resin (based on the active solid content of the untreated resin) and having a basis weight of 65 g / m ² was prepared. The paper is 4.0 m / min. And was passed through a series of seven drying cylinders (drying cylinder temperatures: 55, 75, 95, 105, 20 and 20 ° C.) and dried to a moisture of 3.81%. Prior to testing, all paper samples were oven cured at 80 ° C. for 30 minutes. Normal and wet tensile strength properties were determined using the Hercules method for Paper Strength Testing P8.2a-004 (Tensile Testing). This is a combination of the following methods: ISO 1924 part 2 (1994)-Determination of tensile properties; Constant rate of elongation method, Tappi T 494 om- 1 (revised 2001) Tensile properties of paper and paperboard (using constant speed extension device), SCAN P38: 80 (1980)-Tensile strength, stretching and absorption of tensile energy strength, stretch and tensile energy absorption). The results are shown in Table 1 below.

  For comparison, some papers were prepared without a paper strength enhancer (blank) and other papers were prepared with a commercial wet strength agent. The commercial wet strength agent used was the polyamidoamine-epichlorohydrin (PAE) wet strength agent Kymene® 557H, an azetidinium functional PAE (Europe, supplied by Hercules Incorporated Have been). All PADAA-epichlorohydrin resins were activated by addition of caustic to obtain a resin solution with 3% active solids. In general, the activation procedure was performed as follows: the resin was combined with deionized water and a 10% aqueous solution of NaOH and mixed for at least 30 minutes before use. The paper test results are shown in Table 1 below.

Example 12 FIG. Evaluation of Paper Strength An additional set of papers was prepared to determine the effect of the resin on the wet and normal tensile properties of the paper. The paper preparation procedure was as described in Example 11 (pH 7.5, 50:50 blend of softwood / hardwood bleached kraft pulp, Shopper Leaguer number 35 °, containing 1.0% treated resin. Amount 65 g / m ² , speed 5.0 m / min, moisture 3.2%). The paper test results are shown in Table 2.

Example 13 Evaluation of Paper Strength An additional set of papers was prepared to determine the effect of the resin on the wet and normal tensile properties of the paper. The paper preparation procedure was as described in Example 11 (pH 7.35, 50:50 blend of softwood / hardwood bleached kraft pulp, 34 ° Shopper Leaguer number, 1.0% treated resin and basis weight. Amount 65 g / m ² , speed 5.0 m / min, moisture 2.9%). The paper test results are shown in Table 3.

Example 14 Evaluation of Paper Strength An additional set of papers was prepared to determine the effect of the resin on the wet and normal tensile properties of the paper. The paper preparation procedure was as described in Example 11 (pH 7.2, 50:50 blend of softwood / hardwood bleached kraft pulp, Shopper Leaguer freeness 32 °, containing 1.0% treated resin. And a basis weight of 65 g / m ² , a speed of 5.0 m / min, and a moisture content of 4.3%). The paper test results are shown in Table 4.

Claims (62)

A method for producing a polyalkyldiallylamine-epihalohydrin resin, comprising:
(A) adding a salt of the alkyl diallylamine monomer to the water in the reactor to form a salt aqueous solution of about 30% to about 65%;
(B) purging the aqueous salt solution with an inert gas;
(C) heating the aqueous salt solution to a temperature of about 50 ° C. to about 80 ° C .;
(D) adding the redox initiator system to the aqueous salt solution under an inert atmosphere over about 2 to about 6 hours with stirring;
(E) Concurrently with step (d), at least one comonomer is added to the aqueous salt solution with stirring for about 2 to about 5 hours under an inert atmosphere;
(F) maintaining the contents of the container at about 50 ° C. to about 75 ° C. for a time of about 30 to about 120 minutes, thereby forming a copolymer;
(G) diluting the copolymer with an amount of water, thereby forming a copolymer solution having a solids content of about 9% to about 20%;
(H) adjusting the copolymer solution to a pH of about 7 to about 10;
(I) To the copolymer solution, epihalohydrin is added at a temperature of about 20 ° C. to about 50 ° C. in an amount to provide an epihalohydrin: polymer amine functional group ratio of about 0.85 to about 1.5; (J1) at the same time maintaining the pH at about 8 to about 10 and the temperature at about 20 ° C. to about 50 ° C. for a time of about 2 to about 8 hours; or (j2) at the same time initially adjusting the pH to about 8 to about 10 Adjusted to 10, allowing the pH to fluctuate as low as about 6.5, maintaining the temperature at about 20 ° C. to about 50 ° C. for a time of about 2 to about 8 hours; and (k) The temperature is raised to about 60 ° C. to about 90 ° C. over about 0.5 to about 4 hours, while sufficient acid is added to maintain the pH at about 1 to about 3.
A method involving that. further,
(H1) heating the copolymer solution to a temperature of about 65 ° C. to about 75 ° C .;
(H2) The redox initiator as described above is added to the copolymer solution with stirring over about 20 to about 35 minutes under an inert atmosphere, wherein the redox initiator and copolymer are about 1:20. In a weight percent ratio of about 1:80;
(H3) maintaining the contents of the vessel at about 65 ° C. to about 75 ° C. for a time of about 35 to about 75 minutes; and (h4) cooling the copolymer solution to ambient temperature.
The method of claim 1, comprising:   The alkyl diallylamine monomer is N-methyldiallylamine, N-ethyldiallylamine, Nn-propyldiallylamine, N-isopropyldiallylamine, N-butyldiallylamine, N-tert-butyldiallylamine, N-sec-butyldiallylamine, N-pentyldiallylamine 1, Nn-hexyl diallylamine, N-acetamido diallylamine, N-cyanomethyl diallylamine, N-β-propionamido diallylamine, and N- (2-hydroxyethyl) diallylamine, and mixtures thereof. The method described in 1.   4. The method of claim 3, wherein the alkyl diallylamine monomer is N-methyl diallylamine, N-ethyl diallylamine, or a mixture thereof.   The process according to claim 1, wherein the salt of the alkyl diallylamine monomer is a hydrohalide, phosphate, nitrate or sulfate.   6. The method of claim 5, wherein the hydrohalide salt of the alkyl diallylamine monomer is a hydrochloride salt.   6. The process according to claim 5, wherein the hydrohalide salt is N-methyldiallylamine hydrochloride, N-ethyldiallylamine hydrochloride or N-propyldiallylamine hydrochloride.   6. The method of claim 5, wherein the phosphate is a phosphate of N-methyl diallylamine, a phosphate of N-ethyl diallylamine or a phosphate of N-propyl diallylamine.   6. The process according to claim 5, wherein the nitrate is N-methyldiallylamine nitrate, N-ethyldiallylamine nitrate or N-propyldiallylamine nitrate.   The process according to claim 5, wherein the sulfate is a sulfate of N-methyldiallylamine, a sulfate of N-ethyldiallylamine or a sulfate of N-propyldiallylamine.   The method of claim 1, wherein the aqueous salt solution is about 35% to about 65% aqueous salt solution.   The method of claim 11, wherein the aqueous salt solution is about 40% to about 45% aqueous salt solution.   13. The method of claim 12, wherein the aqueous salt solution is about 42% aqueous salt solution.   The process according to claim 1, wherein the inert gas of step (b) is nitrogen or argon.   The method of claim 1, wherein in step (c), the aqueous salt solution is heated to a temperature of about 50C to about 70C.   16. The method of claim 15, wherein in step (c), the aqueous salt solution is heated to a temperature of about 55C to about 70C.   The method of claim 16, wherein in step (c), the aqueous salt solution is heated to a temperature of about 60C to about 65C.   The method of claim 1, wherein the redox initiator comprises a first initiator solution containing a reducing agent and a second initiator solution containing an oxidizing agent.   The method according to claim 18, wherein the oxidizing agent is selected from peroxide type compounds, tert-butyl hydroperoxide, hydrogen peroxide or mixtures thereof.   20. The method of claim 19, wherein the peroxide type compound is a salt of peroxydisulfuric acid.   21. The method of claim 20, wherein the salt of peroxydisulfuric acid is sodium persulfate, potassium persulfate or ammonium persulfate.   The process according to claim 21, wherein the salt of peroxydisulfate is sodium peroxodisulfate.   15. The method of claim 14, wherein the reducing agent is selected from a divalent or tetravalent sulfur compound or a metal that can exist in a valence state greater than one.   24. The method of claim 23, wherein the divalent or tetravalent sulfur compound is selected from sulfides, sulfites, bisulfites, thiosulfates, hydrosulfites, metabisulfites, or mixtures thereof.   24. The method of claim 23, wherein the metal that can exist in a valence state greater than 1 is cobalt, iron, manganese, copper, or mixtures thereof.   25. The method of claim 24, wherein the reducing agent is sodium metabisulfite.   The method of claim 1, wherein the oxidizing agent is peroxydisulfate and the reducing agent is one of sulfite, bisulfite, or metabisulfite.   28. The method of claim 27, wherein the oxidizing agent is sodium persulfate or ammonium persulfate and the reducing agent is sodium bisulfite or sodium metabisulfite.   30. The method of claim 28, wherein the oxidizing agent is sodium persulfate and the reducing agent is sodium metabisulfite.   The method of claim 18, wherein the reducing agent and oxidizing agent are in a molar ratio of about 1: 0.1 to about 1: 0.9.   The process of claim 1 wherein the redox initiator and monomer are in a ratio of about 1:35 to about 1: 185.   32. The method of claim 31, wherein the redox initiator and monomer are in a ratio of about 1:60 to about 1: 120.   33. The method of claim 32, wherein the redox initiator and monomer are in a ratio of about 1:90.   The method of claim 1, wherein in step (d), the inert atmosphere comprises nitrogen or argon gas.   The process according to claim 1, wherein in step (d), the redox initiator is continuously added.   At least one comonomer is vinyl monomer, alkyl (meth) acrylate, hydroxypropyl methacrylamide (HPMA) and mixtures thereof; more preferably acrylamide, methacrylamide, acrylic acid, methacrylic acid, itaconic acid, and The method of claim 1, wherein the method is selected from a mixture.   37. The method of claim 36, wherein the at least one comonomer is selected from acrylamide, acrylic acid and mixtures thereof.   Alkyl (meth) acrylate is methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, BMH, butyl acrylate, butyl methacrylate, hydroxyalkyl (meth) acrylate, hydroxy 37. The method of claim 36, selected from ethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, styrene, ethylene, glyceryl acrylate, glyceryl methacrylate, and mixtures thereof.   The process of claim 1, wherein at least one comonomer is continuously added.   The method of claim 1, wherein the ADAA salt and the at least one comonomer are in a molar ratio of about 15:85 to about 45:55.   41. The method of claim 40, wherein the ADAA salt and the at least one comonomer are in a molar ratio of about 18:82 to about 40:60.   42. The method of claim 41, wherein the ADAA salt and the at least one comonomer are in a molar ratio of about 34:66.   The method of claim 1, wherein in step (e), the inert atmosphere comprises nitrogen or argon gas.   The method of claim 1, wherein in step (e), the reduced specific viscosity of the copolymer is from about 0.10 dL / g to about 0.45 dL / g.   45. The method of claim 44, wherein in step (e), the reduced specific viscosity of the alkyl diallylamine copolymer is from 0.15 dL / g to about 0.30 dL / g.   46. The method of claim 45, wherein in step (e), the reduced specific viscosity of the alkyl diallylamine copolymer is from 0.20 dL / g to about 0.25 dL / g.   47. The method of claim 46, wherein the reduced specific viscosity of the alkyl diallylamine copolymer is from 0.21 dL / g to about 0.23 dL / g.   The process of claim 1 wherein in step (g) the copolymer solution has a solids content of from about 9 to about 16%.   The method of claim 1, wherein in step (h), the pH of the copolymer solution is from about 7.5 to about 10.   50. The method of claim 49, wherein in step (h), the pH of the copolymer solution is from about 8 to about 10.   The method of claim 1, wherein the epihalohydrin is epichlorohydrin.   The method of claim 1, wherein the ratio of epihalohydrin to polymeric amine is from about 0.95 to about 1.45.   53. The method of claim 52, wherein the ratio of epihalohydrin to polymeric amine is from about 1.0 to about 1.45.   54. The method of claim 53, wherein the ratio of epihalohydrin to polymeric amine is from about 1.10 to about 1.20.   The process according to claim 1, wherein in step (k), the acid is sulfuric acid, nitric acid, phosphoric acid, formic acid, acetic acid and hydrochloric acid.   56. The method of claim 55, wherein in step (k), the mineral acid is hydrochloric acid.   The method of claim 2, wherein in step (h2), the weight percent ratio of redox initiator to copolymer is from about 1:20 to about 1:80.   58. The method of claim 57, wherein in step (h2), the weight percent ratio of redox initiator to copolymer is about 1:25.   The method of claim 2, wherein the redox initiator is continuously added.   A resin comprising the reaction product of the method of claim 1.   A wet paper strength enhancer comprising the resin according to claim 60.   62. A cellulose matrix comprising the resin of claim 61.